CO选择性甲烷化的研究进展

doi:10.16085/j.issn.1000-6613.2021-0114

摘要/Abstract

摘要：

CO选择性甲烷化被认为是适用于低温燃料电池的、最具发展潜力的CO深度去除技术，而该技术大规模应用的关键在于高性能负载型催化剂的开发。本文综述了近些年来CO选择性甲烷化的研究进展，以催化剂的选取和评判标准为起点，着重论述了CO和CO₂甲烷化的反应机理、粒径效应以及载体和助剂对催化剂活性和选择性的影响，最后总结了CO选择性甲烷化的研究并对未来的研究方向进行了展望。分析表明，选取合适的活性组分负载量以及载体和助剂可以大幅度提高催化剂的CO甲烷化活性，而通过氯离子改性以及Ru-Ni双金属的制备来控制金属-载体作用界面则是提高催化剂CO甲烷化选择性的关键。指出对甲烷化反应机理的研究和具有长期稳定性催化剂的开发是未来CO选择性甲烷化研究的重点。

关键词: CO选择性甲烷化, 催化剂, 反应机理, 活性, 粒径效应, 载体

Abstract:

Selective CO methanation is considered as the most promising deep CO removal technology for the low-temperature fuel cells. Furthermore, the key to its wide applications is the development of high-performance supported catalysts. The research progress of selective CO methanation in recent years is reviewed in this article. Starting with the selection and evaluation criteria of catalysts, this article focuse on the reaction mechanism of CO and CO₂ methanation, the effects of particle size, supports and promoters on the catalytic activity and selectivity. Finally, the research on selective CO methanation is summarized and future research direction is also prospected. It is concluded that selecting appropriate loading of active components, supports and promoters can significantly improve the activity of the catalyst. However, the metal-support interface can be controlled by the chloride ion modification and the preparation of Ru-Ni bimetal, which plays a vital role in the improvement of the selectivity. The research on the methanation reaction mechanism and the development of long-term stable catalysts will be the focus of future researches.

Key words: selective CO methanation, catalyst, reaction mechanism, reactivity, particle size effects, support

中图分类号:

TQ426

纪子柯, 包成. CO选择性甲烷化的研究进展[J]. 化工进展, 2022, 41(1): 120-132.

JI Zike, BAO Cheng. Research progress of selective CO methanation[J]. Chemical Industry and Engineering Progress, 2022, 41(1): 120-132.

图/表 17

图1 用于PEMFC的燃料重整制氢系统

图2 CO选择性甲烷化反应体系热力学分析[(b)为(a)中CO浓度的局部放大图；气体组成（体积分数）为1%CO、24%CO2、75%H2；反应压力p=1.01×105Pa]

表1 不同催化剂的CO选择性甲烷化性能

催化剂	反应气体体积分数/%				质量空速	体积空速	T_min	S_min（CO）	T_max	S_max（CO）	参考文献
催化剂	CO	CO₂	H₂	H₂O	/cm³·h^-1·g^-1	/h^-1	/℃	/%	/℃	/%	参考文献
5%Ru/Al₂O₃	0.56	21.7	42.2	He	19800		210	100	244	50	［5］
Ni/ZrO₂	1	20	79	0		8500	215	100	350	50	［6］
3%Ru/50%NiAlO_x/NF	1	20	79	0		250	180	100	280	50	［7］
RuNi/Al₂O₃-CNTs/NF	1	20	79	0		1400	190	100	250	50	［8］
MS/Ni/AlVO_x	0.43	17.1	67.9	14.53		2400	170	100	200	50	［9］
0.22TMS/0.039V/Ni	0.43	17.1	67.9	14.53		4800	164	100	198	50	［10］
Ni/CeO₂（Cl*）	1	20	65	10	29000		240	90	285	50	［11］
Ni（Cl_0.1）/ZrO₂	1	18	70	N₂	15000		215	100	295	50	［12］
Ru-Ni/TiO₂-Al₂O₃	1	20	50	He		2400	210	95	220	80	［13］
1%Ru/MA-40Ni	0.87	17.4	68.73	13		2400	190	100	260	50	［14］

图3 CO解离甲烷化

表2 CO解离甲烷化反应机理

CO直接解离	歧化反应
$C O + * → C O *$	$C O + * → C O *$
$H 2 + 2 * → H * + H *$	$H 2 + 2 * → H * + H *$
$C O * + * → C * + O * (R D S)$	$C O * + C O * → C O 2 + C * + * (R D S)$
$C * + 4 H * → C H 4 + 5 *$	$C * + 4 H * → C H 4 + 5 *$

表2 CO解离甲烷化反应机理

CO直接解离	歧化反应
$C O + * → C O *$	$C O + * → C O *$
$H 2 + 2 * → H * + H *$	$H 2 + 2 * → H * + H *$
$C O * + * → C * + O * (R D S)$	$C O * + C O * → C O 2 + C * + * (R D S)$
$C * + 4 H * → C H 4 + 5 *$	$C * + 4 H * → C H 4 + 5 *$

图4 CO缔合甲烷化

表3 CO缔合甲烷化反应机理

HCO路径		COH路径
	$C O + * → C O *$		$C O + * → C O *$
$C O + * → C O *$	$H 2 + 2 * → H * + H *$	$C O + * → C O *$	$H 2 + 2 * → H * + H *$
$H 2 + 2 * → H * + H *$	$C O * + H * → H C O * + * (R D S)$	$H 2 + 2 * → H * + H *$	$C O * + H * → C O H * + * (R D S)$
$C O * + H * → H C O * + * (R D S)$	$H C O * + H * → H C O H * + *$	$C O * + H * → C O H * + * (R D S)$	$C O H * + H * → H C O H * + *$
$H C O * + * → H C * + O *$	$H C O H * + * → H C * + O H *$	$C O H * + * → C * + O H *$	$H C O H * + H * → C H 2 O H * + *$
$C H * + 3 H * → C H 4 + 4 *$	$C H * + 3 H * → C H 4 + 4 *$	$C * + 4 H * → C H 4 + 5 *$	$C H 2 O H * + * → C H 2 * + O H *$
			$C H 2 * + 2 H * → C H 4 + 3 *$

表3 CO缔合甲烷化反应机理

HCO路径		COH路径
	$C O + * → C O *$		$C O + * → C O *$
$C O + * → C O *$	$H 2 + 2 * → H * + H *$	$C O + * → C O *$	$H 2 + 2 * → H * + H *$
$H 2 + 2 * → H * + H *$	$C O * + H * → H C O * + * (R D S)$	$H 2 + 2 * → H * + H *$	$C O * + H * → C O H * + * (R D S)$
$C O * + H * → H C O * + * (R D S)$	$H C O * + H * → H C O H * + *$	$C O * + H * → C O H * + * (R D S)$	$C O H * + H * → H C O H * + *$
$H C O * + * → H C * + O *$	$H C O H * + * → H C * + O H *$	$C O H * + * → C * + O H *$	$H C O H * + H * → C H 2 O H * + *$
$C H * + 3 H * → C H 4 + 4 *$	$C H * + 3 H * → C H 4 + 4 *$	$C * + 4 H * → C H 4 + 5 *$	$C H 2 O H * + * → C H 2 * + O H *$
			$C H 2 * + 2 H * → C H 4 + 3 *$

图5 不同表面结构上的CO活化路径

图6 CO2解离甲烷化

图7 CO2缔合甲烷化

表4 CO和CO2甲烷化机理的对比

反应类型	反应方式	反应方式判定	活性位点位置	主要中间体	限速步骤	影响因素
CO甲烷化	解离	C－O键断裂是否有H协助	活性金属	C_ad	C_ad的加氢	温度、表面结构
	缔合			HCO_ad	HCO_ad的生成
				COH_ad	COH_ad的生成
CO₂甲烷化	解离	是否生成CO_ad中间体	活性金属	CO_ad	CO_ad的解离	反应气体组成、制备方法、活性组分负载量
	缔合		金属-载体作用界面	CO_ad	CO_ad的生成
			金属-载体作用界面	HCOO_ad	HCOO_ad的加氢

图8 半球模型

图9 Ni的负载量对Ni/MgAl2O4催化剂性能的影响 [48]

图10 V的添加对Ni/Al2O3催化剂性能的影响

图11 Cl掺杂方式对催化剂性能的影响[11]Ni/CeO2(Cl*)—在NH4Cl处理之前负载Ni；Ni(Cl*)/CeO2—NH4Cl处理之后；Ni(Cl)/CeO2—含氯的Ni前体制备；Ni/CeO2—无氯的Ni前体制备

图12 氯离子作用机理

图13 Ru-Ni双金属作用机理[79]

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